CN105582879B - Sulphur arsenic cleanser and preparation method thereof - Google Patents
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Abstract
The present invention relates to a kind of sulphur arsenic cleanser and preparation method thereof, mainly solves sulphur arsenic cleanser heap density height in the prior art, bad mechanical strength, and Sulfur capacity and arsenic hold the problem of low.The present invention is by a kind of sulphur arsenic cleanser, in terms of parts by weight, including following components：A) 13 parts of houghite；B) 1~8 part of aurichalcite；C) 10~50 parts of cupric oxide；D) 10~60 parts of zinc oxide；E) technical solution of 0.01~3 part of rare earth metal R preferably resolves the problem, in the purification available for natural gas, synthesis gas, lightweight liquid state hydro carbons etc..
Description
Technical field
The present invention relates to a kind of sulphur arsenic cleanser and preparation method thereof.
Background technology
The impurity such as sulphur arsenic are widely present in the raw materials such as natural gas, synthesis gas, coal gas, lightweight liquid state hydro carbons, these
The presence of impurity can cause many catalyst poisonings to inactivate, and greatly shorten catalyst life, even resulting in catalytic reaction can not be just
Often carry out；Can be as production be into being advanced into the composite of downstream, so as to bring a system in addition, not removing clean sulphur arsenic impurities
The problem of Environmental Health of row etc..Therefore, remove master of the impurity such as sulphur arsenic for protection downstream unit high-efficiency high-accuracy
The catalyst and quality for improving downstream product at the same time has very important meaning.
Under normal circumstances, the sulphur-containing substance present in the raw material of industry is mainly H2S and COS, for these sulphur-containing substances
Deep removal effect most preferably Zinc oxide desulfurizer.Zinc oxide desulfurization with its desulfurization precision is high, easy to use, safe can
Lean on, sulfur capacity is high, plays " checking on " and " protection " acts on and occupy very important status, it be widely applied to synthesize ammonia,
The industries such as hydrogen manufacturing, coal chemical industry, petroleum refinement, beverage production, to remove natural gas, petroleum distillate, casing-head gas, refinery gas, synthesis
Hydrogen sulfide and some organic sulfurs in the raw materials such as gas, carbon dioxide.Sulphur in unstripped gas can be removed to by zinc sulphide desulfurization
0.055mg/kg.CuO is added in normal temp zinc oxide desulfuriging agent to improve its desulphurizing ability.It is de- that Zinc oxide desulfurizer is generally used for essence
Sulphur process, it can also absorb general organosulfur compound.Arsenic impurities in the raw material of industry, usually with AsH3Form exists, work
The Hydrodearsenic Catalyst used in industry is substantially divided into copper system, four class of lead system, manganese systems and nickel system, wherein relatively conventional with copper system.Copper system takes off
Arsenical arsenic holds height, can be carried out under room temperature, normal pressure and higher space velocity.Copper system Hydrodearsenic Catalyst is divided into metallic copper, CuO-Al again2O3、
CuO-ZnO-Al2O3Deng.When using CuO as active component, AsH3By Cu2+It is reduced at a low price or metallic state, arsenic is combined or swum with copper
From into element state.The development trend of desulfurizing agent and Hydrodearsenic Catalyst be to low bulk density, low temperature in use, high intensity and high sulfur capacity and
The direction that arsenic holds is developed.
Patent CN101591554A discloses a kind of room temperature composite sulfur arsenic cleanser and preparation method thereof, the sulphur arsenic cleanser
It is made of carrier and active component, active component is lead oxide, magnetic iron oxide and cupric oxide, and carrier is γ-Al2O3, the sulphur arsenic
Cleanser needs, when 350~650 DEG C of activation 4~8 are small, it is net to can be seen that the oxide sulphur arsenic from its composition and preparation method
Agent heap density is high, and preparation process is complicated, and commercial Application cost is higher.
Patent CN102049236A discloses a kind of copper zinc ambient temperature desulfuration agent and preparation method thereof, which is by alkali formula
Zinc carbonate, basic copper carbonate and binding agent composition, the preparation of the desulfurization sulfur agent is by commercially available basic zinc carbonate, basic carbonate
Copper, binding agent and water are mediated, are molded, being obtained after drying, which is obtained by physical mixed, thus zinc-copper therein
Active component can not play synergistic effect, so as to cause its Sulfur capacity relatively low.
The content of the invention
The technical problems to be solved by the invention are that sulphur arsenic cleanser heap density is high in the prior art, bad mechanical strength, sulphur
Hold and arsenic holds the problem of low, there is provided a kind of new sulphur arsenic cleanser and preparation method thereof.The sulphur arsenic cleanser contains aurichalcite
And CuO-ZnO class solid solution, there is the advantages of heap density is low, high mechanical strength, Sulfur capacity and high arsenic appearance.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：By a kind of sulphur arsenic cleanser, with weight
Number meter, including following components：A) 1-3 parts of houghite；B) 1~8 part of aurichalcite；C) 10~50 parts of cupric oxide；
D) 10~60 parts of zinc oxide；E) 0.01~3 part of rare earth metal R.
In above-mentioned technical proposal, in terms of sulphur arsenic cleanser parts by weight, the preferred scope of the houghite is 1~2 part；
The preferred scope of the aurichalcite is 2~7 parts；The preferred scope of the cupric oxide is 13~48；The zinc oxide zinc it is excellent
It is 15~55 parts to select scope；The preferred scope of the rare earth metal R is 0.02~2 part；The preferred lanthanum of selected rare earth metal, cerium, yttrium
At least one of；The heap density of the sulphur arsenic cleanser is less than 1.0kg/m3, side pressure strength is more than 80N/.
In above-mentioned technical proposal, houghite is [CuyZn(1-x-y)Alx(OH)2](CO3)x/2.mH2O), x is Al/ (Zn+Cu
+ Al) molar ratio, x for 0.2~0.33, m be hydration number；X is preferably 0.25；Cu:Zn:Al molar ratios are preferably 3:3:2
Or 2:4:2.
The preparation method of the sulphur arsenic cleanser, in turn includes the following steps：
(1) by copper nitrate, zinc nitrate, aluminum nitrate, the nitrate of R and hydromassage, your ratio is counted：Cu/Zn is 0.1~2；Al/Zn
For 0~0.8；R/ (Cu+Zn+Al) is 0.002~1；(Cu+Zn+Al)/H2The ratio that O is 0.01~0.04 mixes, and stirs evenly
Obtain solution I；
(2) by least one of sodium carbonate, sodium acid carbonate, ammonium carbonate and hydromassage that than the ratio for 0.01~0.04
Mixing, stirs evenly to obtain solution II；
(3) solution I and II is uniformly mixed, at 40~90 DEG C, reaction 0.5~3 obtains sediment when small, and sediment is washed
It is dry；
(4) sediment, binding agent, mix lubricant are rolled to the water for uniformly adding 10~50 weight %, are granulated；State viscous
Knot agent is at least one of aluminium oxide, alumina cement and cellulose；The lubricant is graphite, talcum powder, sesbania powder and hard
At least one of resin acid.
(5) by the powder being granulated at 170~300 DEG C, when roasting 1~5 is small；
(6) compression molding is sulphur arsenic cleanser；
(7) sulphur arsenic cleanser is washed and dried.
Sulphur arsenic cleanser of the present invention, using special preparation process, makes it contain houghite phase [CuyZn(1-x-y)
Alx(OH)2](CO3)x/2.mH2O), due to the special interlayer hydroxyl structure of houghite so that with tighter between cleanser each component
Close mode connects, thus the sulphur arsenic cleanser has more high mechanical properties.Meanwhile the sulphur arsenic cleanser contains aurichalcite,
Its volume is larger, and larger duct can be produced in banking process, thus its heap density is relatively low.Formed after aurichalcite heat treatment
CuO-ZnO class solid solution, arrange in such solid solution more ZnO around CuO, similarly, around ZnO has also arranged more
CuO, it is ensured that CuO and ZnO are fully refined so that the chance of CuO particles and ZnO particle interracial contact greatly increases, there is provided
More activated centres.The addition of rare earth metal, improves the distribution of charges around Zn, Cu, is conducive to carrying for its detergent power
It is high.The present invention achieves preferable technique effect.
Room temperature sulphur arsenic cleanser of the present invention can be used in the purification of natural gas, synthesis gas, lightweight liquid state hydro carbons etc..
In room temperature, normal pressure, volume space velocity 1500h-1Under conditions of, with sulphur containing various concentrations, the nitrogen of arsenic compound impurity or synthesis
Gas is by reactor, and the Sulfur capacity of cleanser is up to more than 20%.In room temperature, pressure 3.0MPa, mass space velocity 3.5h-1Bar
It is also reachable by reactor, the Sulfur capacity arsenic appearance of cleanser with the propylene liguid of sulphur containing various concentrations, arsenic compound impurity under part
More than 20%.
Below by embodiment, the invention will be further elaborated.
Brief description of the drawings
Fig. 1 is the XRD diffraction spectrograms for preparing cleanser.(characteristic diffraction peak of houghite is at peak in 2 θ=13.0 °；It is green
The characteristic diffraction peak of copper zinc ore is in 2 θ=13.0 °；The diffraction maximum of cupric oxide is 2 θ=35.49 ° and 38.73 °；The feature of zinc oxide
Diffraction maximum is in 2 θ=31.8 °, 36.2 ° and 56.6 °)
Embodiment
【Comparative example 1】
1 synthetic sample of comparative example is zinc oxide.
500 kilograms of 125 kilograms of zinc nitrate and water are mixed evenly to obtain metal salt solution, by 49 kilograms of sodium carbonate and
550 kilograms of water, which is uniformly mixed, obtains sodium carbonate liquor, and sodium carbonate liquor is uniformly mixed with metal salt solution, reacts 1 at 70 DEG C
Hour, sediment is washed into drying, adds 14 kilograms of aluminium oxide, 1 kilogram of graphite mixing rolls, and then adds 30 weight %'s
Water, is granulated, and when 300 DEG C of roastings 3 are small, compression molding, obtains sample composition and be shown in Table 1.
【Comparative example 2】
2 synthetic sample of comparative example is cupric oxide.
500 kilograms of 101 kilograms of copper nitrate and water are mixed evenly to obtain metal salt solution, by 49 kilograms of sodium carbonate and
550 kilograms of water, which is uniformly mixed, obtains sodium carbonate liquor, and sodium carbonate liquor is uniformly mixed with metal salt solution, reacts 1 at 70 DEG C
Hour, sediment is washed into drying, adds 14 kilograms of aluminium oxide, 1 kilogram of graphite mixing rolls, and then adds 30 weight %'s
Water, is granulated, and when 300 DEG C of roastings 3 are small, compression molding, obtains sample composition and be shown in Table 1.
【Comparative example 3】
3 synthetic sample of comparative example is the cupric oxide zinc oxide without hydrotalcite and aurichalcite.
By 45 kilograms of copper nitrate, 56 kilograms of zinc nitrate, 500 kilograms of 16 kilograms of aluminum nitrate and water are mixed evenly to obtain gold
Belong to salting liquid, 550 kilograms of 50 kilograms of sodium carbonate and water are uniformly mixed and obtain sodium carbonate liquor, by sodium carbonate liquor and metal salt
Solution is uniformly mixed, and when 70 DEG C of reactions 1 are small, sediment is washed drying, adds 10 kilograms of aluminium oxide, 1 kilogram of graphite mixing
Roll, then add the water of 30 weight %, be granulated, when 350 DEG C of roastings 5 are small, compression molding, obtains sample composition and be shown in Table 1.
【Comparative example 4】
4 synthetic sample of comparative example is the cleanser without rare earth metal.
By 45 kilograms of copper nitrate, 56 kilograms of zinc nitrate, 500 kilograms of 16 kilograms of aluminum nitrate and water are mixed evenly to obtain gold
Belong to salting liquid, 550 kilograms of 50 kilograms of sodium carbonate and water are uniformly mixed and obtain sodium carbonate liquor, by sodium carbonate liquor and metal salt
Solution is uniformly mixed, and when 70 DEG C of reactions 1 are small, sediment is washed drying, adds 10 kilograms of aluminium oxide, 1 kilogram of graphite mixing
Roll, then add the water of 30 weight %, be granulated, when 350 DEG C of roastings 5 are small, compression molding, obtains sample composition and be shown in Table 1.
【Embodiment 1】
By 45 kilograms of copper nitrate, 56 kilograms of zinc nitrate, 16 kilograms of aluminum nitrate, the 500 kilograms of mixing of 1.5 kilograms of cerous nitrate and water
Metal salt solution is uniformly mixing to obtain, 550 kilograms of 50 kilograms of sodium carbonate and water are uniformly mixed and obtain sodium carbonate liquor, by carbonic acid
Sodium solution is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, will add 10 kilograms of oxidations after sediment washing drying
Aluminium, 1 kilogram of graphite mixing roll, then add the water of 30 weight %, be granulated, and when 270 DEG C of roastings 2 are small, compression molding, will be molded
Sample is with water with solid-liquid weight ratio 1：When 3 ratio mixing 1 is small, then filter, sample is obtained when 110 DEG C of dryings 12 are small
Composition is shown in Table 1.
【Embodiment 2】
45 kilograms of copper nitrate, 56 kilograms of zinc nitrate, 16 kilograms of aluminum nitrate, 500 kilograms of 0.03 kilogram of cerous nitrate and water is mixed
Conjunction is uniformly mixing to obtain metal salt solution, is uniformly mixed and obtains sodium carbonate liquor 550 kilograms of 50 kilograms of sodium carbonate and water, by carbon
Acid sodium solution is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, will add 10 kilograms of oxidations after sediment washing drying
Aluminium, 1 kilogram of graphite mixing roll, then add the water of 30 weight %, be granulated, and when 270 DEG C of roastings 2 are small, compression molding, will be molded
Sample is with water with solid-liquid weight ratio 1：When 3 ratio mixing 1 is small, then filter, sample is obtained when 110 DEG C of dryings 12 are small
Composition is shown in Table 1.
【Embodiment 3】
45 kilograms of copper nitrate, 56 kilograms of zinc nitrate, 16 kilograms of aluminum nitrate, 500 kilograms of 0.15 kilogram of cerous nitrate and water is mixed
Conjunction is uniformly mixing to obtain metal salt solution, is uniformly mixed and obtains sodium carbonate liquor 550 kilograms of 50 kilograms of sodium carbonate and water, by carbon
Acid sodium solution is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, will add 10 kilograms of oxidations after sediment washing drying
Aluminium, 1 kilogram of graphite mixing roll, then add the water of 30 weight %, be granulated, and when 270 DEG C of roastings 2 are small, compression molding, will be molded
Sample is with water with solid-liquid weight ratio 1：When 3 ratio mixing 1 is small, then filter, sample is obtained when 110 DEG C of dryings 12 are small
Composition is shown in Table 1.
【Embodiment 4】
45 kilograms of copper nitrate, 56 kilograms of zinc nitrate, 16 kilograms of aluminum nitrate, 500 kilograms of 0.75 kilogram of cerous nitrate and water is mixed
Conjunction is uniformly mixing to obtain metal salt solution, is uniformly mixed and obtains sodium carbonate liquor 550 kilograms of 50 kilograms of sodium carbonate and water, by carbon
Acid sodium solution is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, will add 10 kilograms of oxidations after sediment washing drying
Aluminium, 1 kilogram of graphite mixing roll, then add the water of 30 weight %, be granulated, and when 270 DEG C of roastings 2 are small, compression molding, will be molded
Sample is with water with solid-liquid weight ratio 1：When 3 ratio mixing 1 is small, then filter, sample is obtained when 110 DEG C of dryings 12 are small
Composition is shown in Table 1.
【Embodiment 5】
45 kilograms of copper nitrate, 56 kilograms of zinc nitrate, 16 kilograms of aluminum nitrate, 500 kilograms of 2.25 kilograms of cerous nitrate and water is mixed
Conjunction is uniformly mixing to obtain metal salt solution, is uniformly mixed and obtains sodium carbonate liquor 550 kilograms of 50 kilograms of sodium carbonate and water, by carbon
Acid sodium solution is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, will add 10 kilograms of oxidations after sediment washing drying
Aluminium, 1 kilogram of graphite mixing roll, then add the water of 30 weight %, be granulated, and when 270 DEG C of roastings 2 are small, compression molding, will be molded
Sample is with water with solid-liquid weight ratio 1：When 3 ratio mixing 1 is small, then filter, sample is obtained when 110 DEG C of dryings 12 are small
Composition is shown in Table 1.
【Embodiment 6】
By 45 kilograms of copper nitrate, 56 kilograms of zinc nitrate, 16 kilograms of aluminum nitrate, the 500 kilograms of mixing of 3.0 kilograms of cerous nitrate and water
Metal salt solution is uniformly mixing to obtain, 550 kilograms of 50 kilograms of sodium carbonate and water are uniformly mixed and obtain sodium carbonate liquor, by carbonic acid
Sodium solution is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, will add 10 kilograms of oxidations after sediment washing drying
Aluminium, 1 kilogram of graphite mixing roll, then add the water of 30 weight %, be granulated, and when 270 DEG C of roastings 2 are small, compression molding, will be molded
Sample is with water with solid-liquid weight ratio 1：When 3 ratio mixing 1 is small, then filter, sample is obtained when 110 DEG C of dryings 12 are small
Composition is shown in Table 1.
【Embodiment 7】
By 45 kilograms of copper nitrate, 56 kilograms of zinc nitrate, 16 kilograms of aluminum nitrate, the 500 kilograms of mixing of 1.5 kilograms of lanthanum nitrate and water
Metal salt solution is uniformly mixing to obtain, 550 kilograms of 50 kilograms of sodium carbonate and water are uniformly mixed and obtain sodium carbonate liquor, by carbonic acid
Sodium solution is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, will add 10 kilograms of oxidations after sediment washing drying
Aluminium, 1 kilogram of graphite mixing roll, then add the water of 30 weight %, be granulated, and when 270 DEG C of roastings 2 are small, compression molding, will be molded
Sample is with water with solid-liquid weight ratio 1：When 3 ratio mixing 1 is small, then filter, sample is obtained when 110 DEG C of dryings 12 are small
Composition is shown in Table 1.
【Embodiment 8】
By 45 kilograms of copper nitrate, 56 kilograms of zinc nitrate, 16 kilograms of aluminum nitrate, the 500 kilograms of mixing of 1.3 kilograms of yttrium nitrate and water
Metal salt solution is uniformly mixing to obtain, 550 kilograms of 50 kilograms of sodium carbonate and water are uniformly mixed and obtain sodium carbonate liquor, by carbonic acid
Sodium solution is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, will add 10 kilograms of oxidations after sediment washing drying
Aluminium, 1 kilogram of graphite mixing roll, then add the water of 30 weight %, be granulated, and when 270 DEG C of roastings 2 are small, compression molding, will be molded
Sample is with water with solid-liquid weight ratio 1：When 3 ratio mixing 1 is small, then filter, sample is obtained when 110 DEG C of dryings 12 are small
Composition is shown in Table 1.
【Embodiment 9】
By 40 kilograms of copper nitrate, 62 kilograms of zinc nitrate, 16 kilograms of aluminum nitrate, the 500 kilograms of mixing of 1.5 kilograms of cerous nitrate and water
Metal salt solution is uniformly mixing to obtain, 550 kilograms of 53 kilograms of sodium carbonate and water are uniformly mixed and obtain sodium carbonate liquor, by carbonic acid
Sodium solution is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, will add 10 kilograms of oxidations after sediment washing drying
Aluminium, 1 kilogram of graphite mixing roll, then add the water of 30 weight %, be granulated, and when 260 DEG C of roastings 5 are small, compression molding, will be molded
Sample is with water with solid-liquid weight ratio 1：When 3 ratio mixing 1 is small, then filter, sample is obtained when 110 DEG C of dryings 12 are small
Composition is shown in Table 1.
【Embodiment 10】
By 40 kilograms of copper nitrate, 62 kilograms of zinc nitrate, 16 kilograms of aluminum nitrate, the 500 kilograms of mixing of 1.5 kilograms of cerous nitrate and water
Metal salt solution is uniformly mixing to obtain, 550 kilograms of 53 kilograms of sodium carbonate and water are uniformly mixed and obtain sodium carbonate liquor, by carbonic acid
Sodium solution is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, will add 10 kilograms of oxidations after sediment washing drying
Aluminium, 1 kilogram of graphite mixing roll, then add the water of 30 weight %, be granulated, and when 270 DEG C of roastings 5 are small, compression molding, will be molded
Sample is with water with solid-liquid weight ratio 1：When 3 ratio mixing 1 is small, then filter, sample is obtained when 110 DEG C of dryings 12 are small
Composition is shown in Table 1.
【Embodiment 11】
By 20 kilograms of copper nitrate, 86 kilograms of zinc nitrate, 16 kilograms of aluminum nitrate, the 500 kilograms of mixing of 1.5 kilograms of cerous nitrate and water
Metal salt solution is uniformly mixing to obtain, 550 kilograms of 53 kilograms of sodium carbonate and water are uniformly mixed and obtain sodium carbonate liquor, by carbonic acid
Sodium solution is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, will add 10 kilograms of oxidations after sediment washing drying
Aluminium, 1 kilogram of graphite mixing roll, then add the water of 30 weight %, be granulated, and when 280 DEG C of roastings 5 are small, compression molding, will be molded
Sample is with water with solid-liquid weight ratio 1：When 3 ratio mixing 1 is small, then filter, sample is obtained when 110 DEG C of dryings 12 are small
Composition is shown in Table 1.
【Embodiment 12】
By 71 kilograms of copper nitrate, 18 kilograms of zinc nitrate, 16 kilograms of aluminum nitrate, the 500 kilograms of mixing of 1.5 kilograms of cerous nitrate and water
Metal salt solution is uniformly mixing to obtain, 550 kilograms of 53 kilograms of sodium carbonate and water are uniformly mixed and obtain sodium carbonate liquor, by carbonic acid
Sodium solution is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, will add 8 kilograms of aluminium oxide after sediment washing drying,
1 kilogram of graphite mixing rolls, and then adds the water of 30 weight %, is granulated, and when 280 DEG C of roastings 5 are small, compression molding will be into pattern
Product are with water with solid-liquid weight ratio 1：When 3 ratio mixing 1 is small, then filter, sample sets are obtained when 110 DEG C of dryings 12 are small
Into being shown in Table 1.
Table 1
【Embodiment 13】
Sulphur arsenic cleanser prepared by above-described embodiment is ground into the particle of 20~40 mesh, it is 1cm to fill it into internal diameter
Reactor in, in room temperature, normal pressure, volume space velocity 1500h-1Under conditions of, with sulphur containing various concentrations, arsenic compound impurity
Nitrogen is evaluated the sulphur arsenic cleanser, the results are shown in Table 2 by the reactor.
Table 2
【Embodiment 14】
Sulphur arsenic cleanser prepared by above-described embodiment is ground into the particle of 20~40 mesh, it is 1cm to fill it into internal diameter
Reactor in, in room temperature, normal pressure, volume space velocity 1500h-1Under conditions of, with sulphur containing various concentrations, arsenic compound impurity
Synthesis gas is evaluated the sulphur arsenic cleanser, the results are shown in Table 3 by the reactor.
Table 3
【Embodiment 15】
Sulphur arsenic cleanser prepared by above-described embodiment is ground into the particle of 20~40 mesh, it is 1cm to fill it into internal diameter
Reactor in, in room temperature, pressure 3.0MPa, mass space velocity 3.5h-1Under conditions of, with sulphur containing various concentrations, arsenic compound
The propylene liguid of impurity is evaluated the sulphur arsenic cleanser, the results are shown in Table 4 by the reactor.
Table 4
Claims (9)
1. a kind of sulphur arsenic cleanser, in terms of parts by weight, including following components：
A) 1-3 parts of houghite；
B) 1~8 part of aurichalcite；
C) 10~50 parts of cupric oxide；
D) 10~60 parts of zinc oxide；
E) 0.01~3 part of rare earth metal R；
The preparation method of the sulphur arsenic cleanser, comprises the following steps successively：
(1) by copper nitrate, zinc nitrate, aluminum nitrate, the nitrate of R and hydromassage, your ratio is counted：Cu/Zn is 0.1~2；Al/Zn is 0
~0.8；R/ (Cu+Zn+Al) is 0.002~1；(Cu+Zn+Al)/H2The ratio that O is 0.01~0.04 mixes, and stirs evenly
Solution I；
(2) by least one of sodium carbonate, sodium acid carbonate, ammonium carbonate and hydromassage that than being mixed for 0.01~0.04 ratio
Close, stir evenly to obtain solution II；
(3) solution I and II is uniformly mixed, at 40~90 DEG C, reaction 0.5~3 obtains sediment when small, sediment is washed dry
It is dry；
(4) sediment, binding agent, mix lubricant are rolled uniformly, with weight of precipitate percentages, adds 10~50 weights
The water of % is measured, is granulated；
(5) by the powder being granulated at 170~300 DEG C, when roasting 1~5 is small；
(6) compression molding is sulphur arsenic cleanser；
(7) sulphur arsenic cleanser is washed and dried.
2. sulphur arsenic cleanser according to claim 1, it is characterised in that in terms of sulphur arsenic cleanser parts by weight, houghite contains
Measure as 1~2 part.
3. sulphur arsenic cleanser according to claim 1, it is characterised in that in terms of sulphur arsenic cleanser parts by weight, aurichalcite contains
Measure as 2~7 parts.
4. sulphur arsenic cleanser according to claim 1, it is characterised in that in terms of sulphur arsenic cleanser parts by weight, aoxidize copper content
For 13~48 parts.
5. sulphur arsenic cleanser according to claim 1, it is characterised in that in terms of sulphur arsenic cleanser parts by weight, zinc oxide content
For 15~55 parts.
6. sulphur arsenic cleanser according to claim 1, it is characterised in that in terms of sulphur arsenic cleanser parts by weight, rare earth metal R
Content is 0.02~2 part.
7. sulphur arsenic cleanser according to claim 1, it is characterised in that rare earth metal R is at least one of lanthanum, cerium, yttrium.
8. sulphur arsenic cleanser according to claim 1, it is characterised in that the heap density of sulphur arsenic cleanser is less than 1.0kg/m3。
9. claim 1~8 any one of them sulphur arsenic cleanser is used for natural gas, synthesis gas, lightweight liquid state hydro carbons
In purification.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0243052A3 (en) * | 1986-04-25 | 1988-12-14 | Imperial Chemical Industries Plc | Sulphur compounds removal |
| CN101327419A (en) * | 2008-08-01 | 2008-12-24 | 中国海洋石油总公司 | Method for preparing catalytic cracking gasoline adsorbing and desulfurizing agent |
| CN101591554A (en) * | 2008-05-30 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of normal temperature composite desulfurating and dearsenic agent and preparation method thereof |
| CN102806065A (en) * | 2011-06-03 | 2012-12-05 | 中国石油化工股份有限公司 | Purifier for adsorbing arsenic hydride and hydrogen phosphide in olefin tail gas and preparation method thereof |
| CN103687667A (en) * | 2011-07-22 | 2014-03-26 | 庄信万丰股份有限公司 | Desulphurisation material comprising copper supported on zinc oxide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0804572D0 (en) * | 2008-03-12 | 2008-04-16 | Johnson Matthey Plc | Preparation of desulphurisation materials |
| US20130026072A1 (en) * | 2011-07-27 | 2013-01-31 | Abdennour Bourane | Catalytic compositions useful in removal of sulfur compounds from gaseous hydrocarbons, processes for making these and uses thereof |
| JP5755999B2 (en) * | 2011-10-31 | 2015-07-29 | 大阪瓦斯株式会社 | Method for producing desulfurizing agent, desulfurizing agent, and method for desulfurizing hydrocarbon |
-
2014
- 2014-10-24 CN CN201410573606.4A patent/CN105582879B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0243052A3 (en) * | 1986-04-25 | 1988-12-14 | Imperial Chemical Industries Plc | Sulphur compounds removal |
| CN101591554A (en) * | 2008-05-30 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of normal temperature composite desulfurating and dearsenic agent and preparation method thereof |
| CN101327419A (en) * | 2008-08-01 | 2008-12-24 | 中国海洋石油总公司 | Method for preparing catalytic cracking gasoline adsorbing and desulfurizing agent |
| CN102806065A (en) * | 2011-06-03 | 2012-12-05 | 中国石油化工股份有限公司 | Purifier for adsorbing arsenic hydride and hydrogen phosphide in olefin tail gas and preparation method thereof |
| CN103687667A (en) * | 2011-07-22 | 2014-03-26 | 庄信万丰股份有限公司 | Desulphurisation material comprising copper supported on zinc oxide |
Non-Patent Citations (1)
| Title |
|---|
| "Cu–Zn–Al mixed metal oxides derived from hydroxycarbonate precursors for H2S removal at low temperature";Dahao Jiang et al.;《Applied Surface Science》;20091205;第256卷;第3216-3223页 * |
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